Oxygen Reduction Reaction Activity Research Articles

Joule heating synthesis for single-atomic Fe sites on porous carbon spheres and armchair-type edge defect engineering dominated oxygen reduction reaction performance

Single-atom catalysts (SACs) embedded in heteroatom-doped carbon are the most promising oxygen reduction reaction (ORR) electrocatalysts. However, the expeditious and facile synthesis of high-performance SACs with Fe-Nx active sites and identifying the role of edge-type defect at the atomic level in carbon support are essential but remain challenging. Herein, Joule heating is applied to anchor Fe single atoms on newly defect rich porous carbon spheres (Fe-N-DCSs) in milliseconds. Fe-N-DCSs achieves exceptional ORR performance, with a half-wave potential (E1/2) of 0.90 V and E1/2 lost of only 20 mV after 30,000 cycles in 0.1 M KOH, and superior Zn-air batteries performances. Density functional theory calculations establish that armchair-type edge defects decorated Fe-N4 active sites boost the desorption of OH* and diminish the ORR overpotential. This work not only provides a speedy route for the fabrication of SACs but also presents new insights into the excellent ORR activity.

Protection of Fe Single‐Atoms by Fe Clusters for Chlorine‐Resistant Oxygen Reduction Reaction

AbstractDirect seawater zinc‐air batteries (S‐ZABs), with their inherent properties of high energy density, intrinsic safety, and low cost, present a compelling avenue for the development of energy storage technology. However, the presence of chloride ions in seawater poses challenges to their air electrode, resulting in sluggish reaction kinetics and poor stability for the oxygen reduction reaction (ORR). Herein, Fe atomic clusters (ACs) decorated Fe single‐metal atoms (SAs) catalyst (FeSA‐FeAC/NC) is prepared using a plasma treatment strategy. The aberration‐corrected transmission electron microscope images confirm the successful construction of Fe SAs surrounding Fe ACs, which delivers robust ORR activity with a half‐wave potential of 0.886 V in alkaline seawater electrolyte. When utilized as the cathode catalyst in assembled S‐ZABs, the battery demonstrates excellent discharge performance, achieving a peak power density of 222 mW cm−2, which is 2.3 times higher than Pt/C based S‐ZABs. Moreover, density functional theory calculations unveil that the synergy effect between the Fe ACs and SAs not only reduces the spin‐down d‐band center in the Fe SAs, but also efficiently suppresses Cl−1 adsorption on Fe SAs due to their strong Cl−1 absorption ability of the Fe ACs, thereby enhancing both the activity and stability of the catalyst.

Carbothermal Reduction-Assisted Synthesis of a Carbon-Supported Highly Dispersed PtSn Nanoalloy for the Oxygen Reduction Reaction.

Exploring high-performance and low-platinum-based electrocatalysts to accelerate the oxygen reduction reaction (ORR) at the air cathode of zinc-air batteries remains crucial. Herein, by combining electroless deposition and carbothermal reduction, a nitrogen-doped carbon-supported highly dispersed PtSn alloy nanocatalyst (PtSn/NC) was prepared for a high-efficiency ORR process. Electrochemical measurements show that PtSn/NC exhibits excellent electrocatalytic ORR activity with a half-wave potential of 0.850 V versus reversible hydrogen electrode (RHE), which is higher than that of commercial Pt/C (0.815 V). The PtSn/NC-based (20 μgPt cm-2) rechargeable Zn-air battery exhibited astonishing performance with a maximum power density of up to 150.1 mW cm-2, as well as excellent rate performance and charge/discharge stability. Physical characterization reveals that carbothermal reduction could compel the transformation of Sn oxide into metallic Sn, which then alloys with the deposited Pt atoms to form the PtSn nanoalloy, in which electrons are transferred from Sn atoms to neighboring Pt atoms, thereby improving the ability of Pt-based active sites to catalyze the ORR process in PtSn/NC by optimizing the unoccupied d-band of Pt atoms. This work provides a reliable and innovative route for the rational design of highly dispersed Pt-based alloy ORR electrocatalysts.

Engineering medium-entropy alloy nanoparticle nanotubes for efficient oxygen reduction

Fuel cells, as promising energy conversion devices, realize the direct conversion of hydrogen fuel chemical energy into electrical energy. The kinetics of cathodic oxygen reduction reaction (ORR) is slow and plays a decisive role in the output efficiency of fuel cells. Platinum catalysts have been commercialized, but their high cost, relatively low catalytic activity and poor cycling durability limit the development of fuel cells. The introduction of non-platinum components is an effective strategy to minimize the cost and maximize the activity. In this study, PtPdCu medium entropy alloy nanoparticle nanotubes (PtPdCu MEANPTs) that demonstrate high catalytic activity and long durability are presented. Combined with density functional theory calculations, the introduction of Pd and Cu modulates surface electronic structure and optimizes the oxygen adsorption energy, thus enhancing the catalytic activity. The 0D/1D hybrid structure exposes more surface sites and inhibits particle maturation. The atomic migration and rearrangement are emerged during the initial stage of potential cycling process, induing a palladium-rich outer layer and preventing the oxidation of platinum atoms. The best-performing Pt24Pd28Cu48 MEANPTs deliver the impressive ORR activity (1.42 A/mgPt at 0.9 V vs. RHE, which is 6.17 times that of commercial Pt/C) and durability (retaining 2.87 times the initial activity of benchmark catalyst after 30,000 potential cycles). Theoretical calculations have confirmed the regulation of alloying on the surface oxygen affinity and revealed the true active sites on the catalyst surface. This work explores the research direction of platinum-based multi-element catalysts with low platinum content and high catalytic activity.

Cobalt Molybdenum Telluride as an Efficient Trifunctional Electrocatalyst for Seawater Splitting

A mixed-metal ternary chalcogenide, cobalt molybdenum telluride (CMT), has been identified as an efficient tri-functional electrocatalyst for seawater splitting, leading to enhanced oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). The CMT was synthesized by a single step hydrothermal technique. Detailed electrochemical studies of the CMT-modified electrodes showed that CMT has a promising performance for OER in the simulated seawater solutions, exhibiting a small overpotential of 385 mV at 20 mA cm−2, and superior catalyst durability for prolonged period of continuous oxygen evolution. Interestingly, while gas chromatography analysis confirmed the evolution of oxygen in an anodic chamber, it showed that there was no chlorine evolution from these electrodes in alkaline seawater, highlighting the novelty of this catalyst. CMT also displayed remarkable ORR activity in simulated seawater as indicated by its four-electron reduction pathway forming water as the dominant product. One of the primary challenges of seawater splitting is chlorine evolution from the oxidation of dissolved chloride salts. The CMT catalyst successfully and significantly lowers the water oxidation potential, thereby separating the chloride and water oxidation potentials by a larger margin. These results suggest that CMT can function as a highly active tri-functional electrocatalyst with significant stability, making it suitable for clean energy generation and environmental applications using seawater.

Grain boundary engineering for efficient and durable electrocatalysis

Grain boundaries in noble metal catalysts have been identified as critical sites for enhancing catalytic activity in electrochemical reactions such as the oxygen reduction reaction. However, conventional methods to modify grain boundary density often alter particle size, shape, and morphology, obscuring the specific role of grain boundaries in catalytic performance. This study addresses these challenges by employing gold nanoparticle assemblies to control grain boundary density through the manipulation of nanoparticle collision frequency during synthesis. We demonstrate a direct correlation between increased grain boundary density and enhanced two-electron oxygen reduction reaction activity, achieving a significant improvement in both specific and mass activity. Additionally, the gold nanoparticle assemblies with high grain boundary density exhibit remarkable electrochemical stability, attributed to boron segregation at the grain boundaries, which prevents structural degradation. This work provides a promising strategy for optimizing the activity, selectivity, and stability of noble metal catalysts through precise grain boundary engineering.

Iron, cobalt embedded nitrogen-doped carbon derived from conjugated macrocyclic polymers as electrocatalysts for oxygen reduction reaction

The synthesis of earth-abundant metal-based electrocatalysts for deploying electrochemical energy devices has become an area of considerable interest. Herein, we have illustrated a facile Friedel-Crafts reaction for designing a metalloporphyrin polymer followed by its calcination to synthesize cauliflower-like nitrogen-doped iron-cobalt bimetallic electrocatalyst (FeCoTpp-900-2) and its satisfactory performance toward reducing oxygen. The bimetallic FeCoTpp-900-2 catalyst exhibits a half-wave potential (E1/2) of 0.84 V (vs. reversible hydrogen electrode (RHE)) and an onset potential (Eonset) of 0.95 V (vs. RHE). The notable electrocatalytic activity for oxygen reduction reaction (ORR) of FeCoTpp-900-2 is attributed to the presence of ORR active nitrogen species along with the Fe-Nx/Co-Nx sites. In addition, FeCoTpp-900-2 possesses an appreciable amount of mesopores responsible for the ORR behavior. Notably, the zinc-air battery consisting of FeCoTpp-900-2 as the catalyst for the air cathode presents a maximal power density of 127.53 mW cm−2 and robust durability for 24 hours (h). Therefore, this work can contribute to the facile synthesis of bimetallic electrocatalysts with non-noble metals to explore their applications in ORR.

Building robust copper nanostructures via carbon coating derived from polydopamine for oxygen reduction reaction

This study explores the synthesis and electrocatalytic performance of copper-nitrogen-carbon composites formed by Cu single atoms/clusters embedded in nitrogen-doped carbon with Cu/Cu2O nanoparticles (Cu-X-NC) for the oxygen reduction reaction (ORR). The catalysts were synthesized using polydopamine as a carbon and nitrogen source via the solvothermal carbonization (STC) method, followed by pyrolysis and acid washing. The effect of solvothermal carbonization temperature (120, 150, and 180 ºC) on the structure and ORR activity was investigated. The physicochemical characterization showed that higher STC temperatures reduced the size of copper crystallites, slightly increased the formation of copper(I) oxide, and led to the creation of well-dispersed copper single atoms/clusters at 150°C. This optimal dispersion enhances the interaction between the copper single atoms and the reactants, leading to faster ORR kinetics, as demonstrated by the lower charge transfer resistance values in electrochemical impedance spectroscopy measurements. Additionally, the balance between micropore and mesopore structures at this temperature facilitates efficient mass transport, which is critical for achieving higher ORR activity. Moreover, accelerated stability tests showed excellent durability for Cu-150-NC, with negligible loss in onset potential after 10,000 cycles. The solvothermal process significantly increased the electrochemically active surface area (ECSA), with Cu-150-NC displaying the highest specific activity and mass activity per gram of copper, indicating superior performance. Overall, these findings underscore the importance of synthesis optimization and provide valuable insights for designing eco-friendly and high-performance copper catalysts for fuel cell applications.

Screening Transition-Metal-Incorporated β-AgVO3 for Augmented Oxygen Reduction Activity.

Exploring cost-effective alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR) in fuel cells is crucial for their large-scale deployment in green energy applications. Silver vanadate (AgVO3) is a well-studied material for photocatalytic applications. Here, we investigate the electrocatalytic ORR activity of the thermodynamically stable β phase of AgVO3 through computational modeling based on DFT. It is found that β-AgVO3 exhibits weak catalytic activity for the ORR, with vanadium being the preferable active site. Incorporating single atoms of transition metals at surface-level vacancies in β-AgVO3 significantly modifies the ORR activity. We study the scaling of free energy changes for the ORR intermediates *OOH, *OH, and *O for various transition metals incorporated, which leads to an optimal overpotential for the system. The optimal overpotential thus obtained is remarkably lower than that of pristine β-AgVO3. For the transition metal atoms we consider here, Co-incorporated β-AgVO3 exhibits the best ORR catalytic activity due to its optimal binding of ORR species to the vanadium site. It is also observed that some of the transition metals considered like Re, Rh, Os, or Mn show weak activity, either due to strong or weak binding. Analysis of the electronic structure of the adsorbate-catalyst interface shows a strong correlation between optimal activity and evolution of midgap states in β-AgVO3, due to transition metal incorporation. Our study concludes that the ORR activity of a stable mixed transition metal oxide like β-AgVO3 can be enhanced with a minimal loading of transition metals, which could help in developing a novel series of ORR catalysts.

Electrocatalysis of Co/CoxOy nanofilms supported by synchronously nitrogen-doped Ketjenblack carbon towards oxygen reduction reaction

Developing a highly active and stable non-precious metal catalyst for oxygen reduction reaction (ORR) is of great practical significance for advancing fuel cell technology. In this work, a continuous two-step hydrothermal reaction followed by high temperature pyrolysis were employed to achieve in situ N-doping preferentially into Ketjenblack carbon (KB-N) and composite of KB-N and Co/CoxOy nanofilms (Co/CoxOy-NFs) as Co/CoxOy-NFs@KB-N. The N-doped state strongly affects the ORR activity of catalyst. All prepared Co/CoxOy-NFs@KB-N catalysts exhibit observably improved ORR activity compared with the basal KB-N and N-doped Co/CoxOy-NFs, in which the optimal Co/CoxOy-NFs@KB-N catalyst demonstrate the positive Eonset (0.864 V) and E1/2 (0.788 V) vs. RHE, the low Tafel slope (69.27 mV dec−1), implying quick ORR kinetics. And, the Co/CoxOy-NFs@KB-N catalyst exhibits highly electrochemical durability. The KB-N substrate can purify Co valence in CoO component, promote amorphization of CoO crystalline structure and enhance the interaction between Co/CoxOy-NFs and KB-N in Co/CoxOy-NFs@KB-N catalyst. Thus electronic effect, structural effect and synergistic effect can strengthen O2 adsorption, provide enough adsorbed sites and accelerate electron transfer, resulting in prominent ORR performance of Co/CoxOy-NFs@KB-N catalyst.

Bifunctional catalytic activity of anion-doped LaSrCoO4 for oxygen reduction and evolution reactions.

Here, we synthesized Co-based, anion-incorporated‍ ‌R‌u‌d‌d‌l‌e‌s-d‌e‌n‌-‌Popper perovskite electrocatalysts (LaSrCoO4-x X y ) and compared their catalytic performances in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The ORR mechanism with the newly synthesized F-doped LaSrCoO4 catalyst was dominated by a four-electron process, and the number of electrons involved in the reaction increased compared with that for LaSrCoO4. The OER activity of the hydride-doped LaSrCoO4 catalyst was the highest among the LaSrCoO4 system catalysts. Density functional theory calculations revealed that there is a correlation between the Co 3d unoccupied orbital band centre and the OER activity. The addition of anions and substitution of metal sites improved the ORR and OER activities of the catalysts. Our findings confirmed that the addition of heteroatom anions can improve the activity of perovskite-type electrocatalysts, promoting their application in various fields.

Defective wood-based chainmail electrocatalysts boost performances of seawater-medium Zn-air batteries

A high-activity and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalyst is critical for seawater-based Zn-air batteries (ZABs). Herein, we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles (Co@D-NCNT/CW) to enhance the ORR/OER activity and stability in seawater medium. During the preparation process, the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material, modulating charge distribution and influencing the adsorption and activation processes. The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion. The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in seawater-based alkaline electrolyte. The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm−2 and a long-term cycling performance over 500 h. The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm−2 and stabilized over 30 h. Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co, optimizing the binding affinity of the Co sites with intermediates and weakening Cl− adsorption. This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures, boosting the development of seawater-based ZABs.

Boosting OER activity of Fe-N Moieties via Ni induced d-Orbital Tailoring for durable rechargeable Zn-Air batteries

Fe-N-C-based catalysts are considered the most promising Pt candidates due to their high oxygen reduction reaction (ORR) activity and low cost, whereas their oxygen evolution reaction (OER) performance is extremely poor due to the sluggish O-O coupling process, which hampers the practical application of rechargeable zinc-air batteries. Here, we in situ infiltrate Ni and Fe ions into metal triazolidine (MET)-derived N-doped porous carbon via a microporous confinement-pyrolysis strategy to enhance the OER activity of the Fe-N sites. The introduction of Ni induced the electronic delocalization of Fe atoms at the Fe-N center, which lowered the adsorption energy barriers for the decisive velocity step (O*→OOH*), thus accelerating the O-O bond coupling and OER kinetics. In addition, the preferential formation of NiOOH at high OER potentials ensures the catalytic stability of zinc-air batteries by trapping Fe ions escaping from carbon corrosion to form FeOOH. The optimized catalyst (FeNi-NC) has an overpotential of only 351 mV at a current density of 50 mA cm−2 under alkaline conditions. More importantly, the assembled ZABs can be stably charged and discharged for more than 500 h at 10 mA cm−2, demonstrating excellent battery charging and discharging stability. This work shows the great potential of strong electronic interactions between polymetals to improve Fe-N-C catalysts.

Development of an efficient bifunctional electrocatalyst based on Co/CoSe2 nanoparticles embedded in N, Se co-doped carbon for AEMFC and rechargeable Zn-air battery

We suggest a hollow-structured N, Se dual-doped carbon framework embedded with Co/CoSe2 nanoparticles (Co/CoSe2@NSeC) as highly efficient bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The prepared electrocatalyst exhibits high electrochemical active surface area attributed to its unique hollow/porous structure and defective heteroatom doping sites. Furthermore, the strongly coupled heterojunction between Co and CoSe2 species not only provides abundant and highly active sites but also generates built-in electric field, thereby promoting electron transfer during the electrocatalytic reaction. Based on the above considerations, the prepared catalyst shows excellent bifunctional electrocatalytic performance. Leveraging the excellent ORR activity of Co/CoSe2@NSeC, alkaline exchange membrane fuel cells (AEMFC) with the Co/CoSe2@NSeC as air cathode exhibits high power density of 171.23 mW cm2. Furthermore, the rechargeable Zn-air battery employing the Co/CoSe2@NSeC shows high specific capacity (729.4 mAh gZn−1), peak power density (192.88 mW cm2), and sustained stability over 300 cycles.

Nitrogen-doped carbon embedded with heterostructured Co3Fe7-Co5.47N nanoalloys for electrocatalytic oxygen reduction reaction in zinc-air battery

The oxygen reduction reaction (ORR) is the cathodic process in zinc-air batteries, but its sluggish kinetics significantly limit the energy conversion efficiency of these batteries. Therefore, developing high-performance ORR electrocatalysts is essential to support the advancement of zinc-air battery technology. Herein, a nitrogen-doped carbon embedded with heterostructured Co3Fe7-Co5.47N nanoalloys (FeCo@NC-900) was fabricated, and its electrocatalytic ORR activity and stability of FeCo@NC-900 were investigated in alkaline media. The FeCo@NC-900 catalyst exhibited a half-wave potential of 0.84 V, a Tafel slope of 76.06 mV·dec−1, and an electron transfer number (n) of approximately 3.83 for ORR. A rechargeable zinc-air battery was assembled using FeCo@NC-900 as the air cathode, achieving an open-circuit voltage of 1.435 V and a maximum power density of 81 mW cm−2, along with good cycling stability.

Cauliflower-like Pd/MoC||Mo2C/C heterostructure as an efficient trifunctional catalyst for formic acid oxidation, hydrogen evolution, and oxygen reduction reactions

The use of Pd-based catalytic materials as electrocatalysts for formic acid oxidation reaction (FAO), hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) has been well-established for some time. The incorporation of a second phase can markedly enhance the electronic properties of the composites. The combination of different compounds with superior electronic properties is crucial for the design and preparation of catalysts with optimal catalytic activity and stability. In this study, a novel cauliflower-like Pd/MoC||Mo2C/C composite with heterostructure is synthesised, which exhibits excellent catalytic activity and long-term stability against FAO, HER, and ORR. The high-temperature treatment results in the formation of small-sized Mo₂C and MoC nanoparticles on the carbonaceous substrate, thereby exposing a greater number of Mo and Mo-C active sites. The formation of heterostructures between Mo₂C and MoC optimises the electronic structure of the composite, thereby facilitating enhanced reaction processes. In terms of FAO, the mass activity of Pd/MoC||Mo2C/C is 1.87A mgPd-1, which is 2.75 times higher than that of Pd/C (0.68A mgPd-1). As for the HER, a much lower overpotential of 28mV is required to achieve a current density of 10mAcm-2 compared to Pd/C (40mV). Fortunately, Pd/MoC||Mo2C/C also shows excellent ORR activity with a half-wave potential of 0.798V and the maximum current density of approximately 5.73mAcm-2 in alkaline electrolyte. These findings may contribute to the development of other noble metal-based materials loaded on intermetallic compounds with stable and effective electrocatalytic performance.

High-performance rechargeable zinc-air batteries enabled by cobalt iron anchored on nitrogen-doped carbon matrix as bifunctional electrocatalyst

Developing efficient bifunctional oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) electrocatalysts is potential ways for achieving high rechargeable zinc-air (Zn-air) battery performance. Herein, we report an iron (II) acetate-assisted strategy to synthesize Co3Fe7-NC-OAc catalyst with cobalt iron (Co3Fe7) alloy anchored on nitrogen-doped carbon (NC) matrix, which can serve as efficient ORR/OER bifunctional electrocatalysts for rechargeable Zn-air batteries. Apart from alloying with Co to form ORR/OER active Co3Fe7 nanoparticles, the incorporation of iron (II) acetate has expanded the pore size inside the Co3Fe7-NC-OAc catalyst to serve as gas transfer channels, and has induced synergetic electronic coupling between Co3Fe7 nanoparticles and NC matrix for boosting catalytic activity. Therefore, Co3Fe7-NC-OAc exhibits favorable ORR activity with a most positive half-wave potential of 0.90 V vs. RHE, fast ORR kinetics with a highest kinetic current density of 57.4 mA cm−2 at 0.85 V vs. RHE, and fast O2 diffusion and transport that enables smaller mass transport overpotential at high current density up to 800 mA cm−2. Additionally, Co3Fe7-NC-OAc can catalyze OER with low overpotential of 310 mV at 10 mA cm−2. When employed as air electrode for Zn-air batteries, Co3Fe7-NC-OAc achieve high peak power densities of 193 mW cm−2 and 587 mW cm−2 in liquid and solid-state Zn-air batteries. The liquid battery also exhibits high specific capacity and remarkable cycling performance. This work opens up a new opportunity for developing highly efficient bifunctional electrocatalysts for Zn-air battery applications.

Nb-doped PrBa 0.8Ca 0.2Co 2O 6-based perovskite cathode with improved oxygen reduction reaction activity and stability for solid oxide fuel cells

Nb-doped PrBa _0.8Ca _0.2Co ₂O ₆-based perovskite cathode with improved oxygen reduction reaction activity and stability for solid oxide fuel cells

Regulating Fe Intermediate Spin States via FeN4‐Cl‐Ti Structure for Enhanced Oxygen Reduction

AbstractModulating the spin states of FeN4 moieties is critical for enhancing the electrocatalytic oxygen reduction reaction (ORR). In this study, Ti4N3Clx and Ti4N3Ox MXenes are synthesized and functionalized with iron phthalocyanine (FePc) to form model catalysts with well‐defined FeN4‐Cl‐Ti and FeN4‐O‐Ti structures, respectively. The FeN4‐Cl‐Ti structure, formed within the Ti4N3Clx/FePc composite, enables precise modulation of FeN4 spin states from low to intermediate spin, significantly enhancing ORR performance. In contrast, the FeN4‐O‐Ti structure in Ti4N3Ox/FePc shows less effective spin state modulation, leading to comparatively lower ORR activity. Compared to FePc and Ti4N3Ox/FePc, Ti4N3Clx/FePc demonstrates superior electrochemical performance, with an ORR half‐wave potential of +0.91 V versus RHE and doubled power densities in Zn–air batteries (214.5 mW cm−2). Theoretical studies confirm that the intermediate spin states induced by the weak‐field ligand‐modified FeN4‐Cl‐Ti structure in Ti4N3Clx/FePc facilitate electron filling in the antibonding orbital composed of Fe 3dz2 and O2 π* orbitals, greatly enhancing O₂ activation and ORR activity. These findings underscore the superior catalytic properties of FeN4‐Cl‐Ti compared to FeN4‐O‐Ti, advancing the understanding of spin state‐related catalytic mechanisms and guiding the design of high‐performance ORR catalysts.

Co2P/CoP embedded in N, P, S triply-doped hollow carbon towards enhanced oxygen electrocatalysis

Simultaneously dispersing phosphide crystallites and multiple heteroatoms in hollow carbon is a significant yet challenging task for achieving high-performance oxygen electrocatalysts of zinc-air batteries. Herein, a simple wrapping-pyrolysis strategy is proposed to prepare Co2P/CoP embedded in N, P, S triply-doped hollow carbon (Co2P/CoP@NPS-HC). Co2P/CoP@NPS-HC composite features hollow polyhedral structure populated with numerous catalytically active Co2P/CoP nanoparticles and N, P, S heteroatoms. This optimized catalyst exhibits excellent activity for oxygen reduction reaction, with a half-wave potential of 0.82 V vs. RHE, and impressive enhancement for oxygen evolution reaction, indicated by an overpotential of 400 mV at 10 mA cm−2. Moreover, Co2P/CoP@NPS-HC catalyst exhibits greater durability and superior methanol tolerance compared to commercial Pt/C. The excellent bifunctional electrocatalytic performance of Co2P/CoP@NPS-HC catalyst is attributed to the synergistic effect of uniformly dispersed Co2P/CoP nanoparticles and N, P, S triply-doped hollow carbon structure. The former provides abundant catalytically active sites, while the latter offers a high accessible specific surface area, as well as enhances catalytic activity and electronic conductivity due to its altered charge distribution.